US4463011A - Bis-imidazolyl-bis-phenylmethane derivatives and their use as fungicides - Google Patents

Bis-imidazolyl-bis-phenylmethane derivatives and their use as fungicides Download PDF

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US4463011A
US4463011A US06/341,634 US34163482A US4463011A US 4463011 A US4463011 A US 4463011A US 34163482 A US34163482 A US 34163482A US 4463011 A US4463011 A US 4463011A
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sub
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imidazolyl
bis
phenyl
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Masaru Ogata
Katsuya Tawara
Yoshihachi Watanabe
Hiroshi Matsumoto
Toshio Takahashi
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Shionogi and Co Ltd
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Shionogi and Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/06—Oxalic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/10—Succinic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/255—Tartaric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/265—Citric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
    • C07C65/10—Salicylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • This invention relates to novel benzylimidazole derivatives useful as an antimycotic drug or agricultural fungicide.
  • Such compounds are, for example, disclosed in Japanese Unexamined Patent Publication No. 50-148357 and the European Journal of Medicinal Chemistry 14, No. 3, pp 227 ⁇ 230, 231 ⁇ 237, 243 ⁇ 245 (1979).
  • the compounds of the following formula (I) are novel. ##STR4## wherein X is halogen, nitro, C 1 to C 5 alkyl, C 1 to C 5 alkoxy or halo-benzyloxy;
  • n is an integer of 0 to 3;
  • Y is oxa, thia or imino optionally substituted by C 1 to C 5 alkanoyl, C 1 to C 5 halo-alkanoyl or C 1 to C 5 alkyl;
  • R 1 is C 1 to C 5 alkyl, C 3 to C 10 dialkylaminoalkyl, C 15 to C 20 dibenzylaminoalkyl, 1-pyrrolidinyl, 2-imidazolin-2-yl, or a group of --(CH 2 )n--Z--Q
  • n is an integer of 0 to 4; Z is oxa, thia, or a single bond; Q is phenyl or thienyl optionally substituted by 1 to 3 members selected from halogen, nitro, C 1 to C 5 alkyl, and C 1 to C 5 alkoxy);
  • ##STR5## is methylene, 1-(1-imidazolyl)-1-methylmethylene, 1-(1-imidazolyl)-1-phenylmethylene, 1-phenylmethylene, or C 1 to C 5 alkylidene optionally substituted by phenyl;
  • halogen means chloro, bromo, fluoro and iodo, preferably chloro.
  • C 1 to C 5 Alkyl means methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, isopentyl, and the like and
  • C 1 to C 5 alkoxy means methoxy, ethoxy, propoxy, isopropoxy, butyloxy, sec-butyloxy, pentyloxy, isopentyloxy, and the like.
  • C 1 to C 5 Alkanoyl means formyl, acetyl, propionyl, butyryl, and the like.
  • C 3 to C 10 Dialkylaminoalkyl means dimethylaminoethyl, diethylaminoethyl, dipropylaminobutyl, methylethylaminoethyl, and the like.
  • C 1 to C 5 Alkylidene means methylene, ethylidene, propylidene, isopropylidene, butylidene, pentylidene, and the like.
  • Compounds (I) can be easily converted to the corresponding pharmaceutically acceptable acid addition salts, which are included within the scope of this invention.
  • Representative acids which can form the pharmaceutically acceptable salts are organic acids such as acetic acid, citric acid, tartaric acid, methanesulfonic acid, malic acid, succinic acid, oxalic acid, salicylic acid, or the like and inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, or the like.
  • A is halogen or an ester residue
  • B and D each is hydrogen or alkyl
  • This process may be carried out by reacting Compound (II) with Compound (III) in the presence of a base in an inert solvent at room temperature or under heating.
  • bases are sodium hydroxide, potassium hydroxide, sodium hydride, sodium amide, potassium amide, sodium ethoxide, potassium carbonate, and the like.
  • Representative inert solvents are dimethylformamide, benzene, methanol, chloroform, dioxane, tetrahydrofuran, acetone, and the like.
  • the starting compound (II) is available, for example, by treating the ketone (IV) with N,N'-thionyldiimidazole or N,N'-carbonyldiimidazole for imidazole formation.
  • the reaction is carried out in an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, dioxane, benzene, acetonitrile, or 1,2-dichloroethane at room temperature or under cooling.
  • reaction of the starting compound (IV) with the compound (III) may be carried out in the same manner as in the First Step. Then the intermediate (V) is subjected to the imidazole formation in the same manner as in the above preparation of the starting compound (II).
  • Compounds (I) and the pharmaceutically acceptable salts thereof prepared in this invention exhibit excellent antimycotic activities and are useful as an antimycotic drug for humans and animals.
  • MIC Minimum Inhibitory Concentration
  • Compounds (I) and their acid addition salts exhibit excellent antifungal activities against various phytopathogenic fungi and soil borne pathogens and are useful as agricultural fungicides.
  • a seed of cucumber (cultivar:Matsukaze) was sown in a vinyl chloride-cup of 9 cm in diameter containing soil in a greenhouse and cultivated.
  • a seed of cucumber (cultivar:Matsukaze) was sown in a vinyl chloride-cup of 9 cm in diameter containing soil in a greenhouse and cultivated.
  • 2.5 ml each of the solution containing a prescribed concentration of the test compound was applied over the above cucumber, which was kept at 25° to 26° C. in 80% humidity for 24 hours.
  • a suspension of Botrytis cinerea spores was inoculated onto the leaves at five spots per leaf and the leaves were kept at 80° C. in 95% humidity for 72 hours.
  • a seed of cucumber (cultivar:Matsukaze) was sown on a vinyl chloride-cup of 9 cm in diameter in a greenhouse containing soil and cultivated.
  • 2.5 ml each of the solution containing a prescribed concentration of the test compound was applied over the above cucumber, which was kept at 25° to 26° C. in 80% humidity for 24 hours.
  • a suspension of Colletotrichum lagenarium spores was inoculated onto the above leaves at five spots per leaf and the leaves were kept at 25° C. in 95% humidity for 1 day and at 25° C. in 75 to 80% humidity for 6 days.
  • a seed of cucumber (cultivar:Matsukaze) was sown in a vinyl chloride-cup of 9 cm in diameter containing soil in a greenhouse and cultivated.
  • 5 ml each of a solution of the test compound in a prescribed concentration was applied over the above cucumber, which was kept at 25° to 26° C. for 1 day.
  • Primary leaves of cucumber previously infected by pathogenic fungi of the powdery mildew (Shpaerotheca fuliginea) were taken and those having lesions covered with spores were cut out in 1 square centimeter pieces, which were stuck to the primary leaves in the cups for inoculation, four plots per leaf.
  • the above treated leaves were kept at 25° to 26° C. for 10 days.
  • Seedlings of rice plants (cultivar:Aichi-asahi) reared in a greenhouse for 10 days were transplanted in a vinyl chloride-cup of 9 cm in diameter.
  • a solution of the test compound at a prescribed concentration was applied to the above rice plants 14 days after the transplanting.
  • a spore suspension of pathogenic fungi of rice plant blast (Pyricularia oryzae) sprayed on the leaf blades of the seedlings, which were kept at 28° C. in 98% humidity for 24 hours and at 28° C. in 90% humidity for 7 days in a greenhouse. The number of infected spots on the inoculated leaves was observed.
  • Compounds (I) or the salts thereof may be applied in a wide variety of oral or parenteral dosage forms solely or in admixture with additives such as diluents, carriers, dispersants and the like.
  • the pharmaceutical compositions may be in the form of solutions, suspensions, powders, granules, tablets, injections, ointments, tinctures, and the like.
  • the formulations may be dispensed in a conventional manner.
  • Compounds (I) may be administered at a dose of 100 to 2000 mg per day for enteral application.
  • compounds (I) and the salts thereof exhibit an excellent control effect against the following phyto-pathogenic fungi and other soil borne pathogens.
  • Grape gray rust, ripe rot, downy mildew, leaf spot, white rot, gray mold, powdery mildew
  • Apple Alternaria leaf spot, canker, black spot, red spot, blossom blight
  • Cucumber downy mildew, anthracnose, sclerotinia rot, gray mold, powdery mildew
  • Compounds (I) or the salts thereof may be formed to wettable powders, granules, powders, emulsions, tablets, aerosols, fumigations, oils, and the like solely or into admixture with additives or carriers ordinarily employed in agricultural fungicides.
  • Compounds (I) may be applied to plants at a dose of 0.5 to 100 g per are.
  • N,N'-thionyldiimidazole prepared from 2.95 g of imidazole and 1.29 g of thionyl chloride in 15 ml of dry methylene chloride is added 2.0 g of Compound (4), and the mixture is extracted with methylene chloride. The organic layer is washed with water, dried over Glauber's salt, and concentrated. The residue is chromatographed on a column of silica gel, which is eluted with methylene chloride to recover 750 mg of unreacted Compound (4).
  • the preparations for fungicides are as follows:
  • a mixture of Compound (3) hydrochloride prepared in Example 1 (5 weight parts), clay (85 weight parts), and talc (10 weight parts) is pulverized and formulated into a dust.
  • a mixture of a compound prepared in Example 8 (50 weight parts), diatomaceous earth (45 weight parts), and calcium alkylbenzenesulfonate (2.5 weight parts) is pulverized, admixed, and formulated into a wettable powder.
  • a mixture of the compound prepared in Example 27 (30 weight parts), xylene (60 weight parts), and polyoxyethylene alkyl aryl ether (10 weight parts) is admixed and formulated into an emulsion.
  • a mixture of the compound prepared in Example 48 (50 weight parts), diatomaceous earth (45 weight parts), and calcium alkylbenzenesulfonate (2.5 weight parts) is pulverized, admixed, and formulated into a wettable powder.
  • a mixture of the compound prepared in Example 7 (30 weight parts), xylene (60 weight parts), and polyoxyethylene alkyl aryl ether (10 weight parts) is admixed and formulated into an emulsion.
  • Example 62 The compound prepared in Example 62 (10 weight parts) is dissolved in water (90 weight parts) to give a solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

Benzylimidazole derivatives of the formula: ##STR1## wherein X is halogen, nitro, alkyl, alkoxy, or halobenzyloxy;
m is an integer of 0 to 3;
Y is oxa, thia or substituted- or unsubstituted-imino;
R1 is alkyl, dialkylaminoaklyl, dibenzylaminoalkyl, 1-pyrrolidinyl, 2-imidazolin-2-yl, or a group of --(CH2)n--Z--Q
(wherein n is an integer of 0 to 4; Z is oxa, thia, or a single bond; and Q is substituted- or unsubstituted-phenyl or thienyl) ##STR2## is methylene, 1-(1-imidazolyl)-1-methylmethylene, 1-(1-imidazolyl)-1-phenylmethylene, 1-phenylmethylene, or substituted or unsubstituted alkylidene;
the benzene ring of the above formula being optionally condensed with another benzene ring
with the proviso that when ##STR3## is methylene said benzene ring is condensed with another benzene ring, and acid addition salts thereof which are useful as an antimycotic drug or agricultural fungicide.

Description

This application is a divisional of copending application Ser. No. 157,166, filed on June 6, 1980, now U.S. Pat. No. 4,328,348, which issued on May 4, 1982.
SUMMARY OF THE INVENTION
This invention relates to novel benzylimidazole derivatives useful as an antimycotic drug or agricultural fungicide. Such compounds are, for example, disclosed in Japanese Unexamined Patent Publication No. 50-148357 and the European Journal of Medicinal Chemistry 14, No. 3, pp 227˜230, 231˜237, 243˜245 (1979). But the compounds of the following formula (I) are novel. ##STR4## wherein X is halogen, nitro, C1 to C5 alkyl, C1 to C5 alkoxy or halo-benzyloxy;
m is an integer of 0 to 3;
Y is oxa, thia or imino optionally substituted by C1 to C5 alkanoyl, C1 to C5 halo-alkanoyl or C1 to C5 alkyl;
R1 is C1 to C5 alkyl, C3 to C10 dialkylaminoalkyl, C15 to C20 dibenzylaminoalkyl, 1-pyrrolidinyl, 2-imidazolin-2-yl, or a group of --(CH2)n--Z--Q
(wherein n is an integer of 0 to 4; Z is oxa, thia, or a single bond; Q is phenyl or thienyl optionally substituted by 1 to 3 members selected from halogen, nitro, C1 to C5 alkyl, and C1 to C5 alkoxy); ##STR5## is methylene, 1-(1-imidazolyl)-1-methylmethylene, 1-(1-imidazolyl)-1-phenylmethylene, 1-phenylmethylene, or C1 to C5 alkylidene optionally substituted by phenyl;
the benzene ring of the above formula being optionally condensed with another benzene ring
with the proviso that when ##STR6## is methylene said benzene ring is condensed with another benzene ring, and pharmaceutically acceptable acid addition salts thereof.
DETAILED EXPLANATION
In the above general formula, halogen means chloro, bromo, fluoro and iodo, preferably chloro. C1 to C5 Alkyl means methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, isopentyl, and the like and C1 to C5 alkoxy means methoxy, ethoxy, propoxy, isopropoxy, butyloxy, sec-butyloxy, pentyloxy, isopentyloxy, and the like. C1 to C5 Alkanoyl means formyl, acetyl, propionyl, butyryl, and the like. C3 to C10 Dialkylaminoalkyl means dimethylaminoethyl, diethylaminoethyl, dipropylaminobutyl, methylethylaminoethyl, and the like. C1 to C5 Alkylidene means methylene, ethylidene, propylidene, isopropylidene, butylidene, pentylidene, and the like.
Compounds (I) can be easily converted to the corresponding pharmaceutically acceptable acid addition salts, which are included within the scope of this invention. Representative acids which can form the pharmaceutically acceptable salts are organic acids such as acetic acid, citric acid, tartaric acid, methanesulfonic acid, malic acid, succinic acid, oxalic acid, salicylic acid, or the like and inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, or the like.
PREPARATION
Compounds (I) may be prepared according to the following scheme: ##STR7## (wherein M is hydrogen or alkali metal;
A is halogen or an ester residue;
B and D each is hydrogen or alkyl; and
X, m, Y, R1, R2 and R3 each has the same significance as given earlier)
(First Step)
This process may be carried out by reacting Compound (II) with Compound (III) in the presence of a base in an inert solvent at room temperature or under heating. Representative bases are sodium hydroxide, potassium hydroxide, sodium hydride, sodium amide, potassium amide, sodium ethoxide, potassium carbonate, and the like. Representative inert solvents are dimethylformamide, benzene, methanol, chloroform, dioxane, tetrahydrofuran, acetone, and the like.
The starting compound (II) is available, for example, by treating the ketone (IV) with N,N'-thionyldiimidazole or N,N'-carbonyldiimidazole for imidazole formation. The reaction is carried out in an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, dioxane, benzene, acetonitrile, or 1,2-dichloroethane at room temperature or under cooling.
(Second Step)
The reaction of the starting compound (IV) with the compound (III) may be carried out in the same manner as in the First Step. Then the intermediate (V) is subjected to the imidazole formation in the same manner as in the above preparation of the starting compound (II).
EFFECT
Compounds (I) and the pharmaceutically acceptable salts thereof prepared in this invention exhibit excellent antimycotic activities and are useful as an antimycotic drug for humans and animals.
Minimum Inhibitory Concentration (MIC, μ/ml) in vitro of some typical Compounds (I) are indicated in the following Table 1. The compound numbers correspond to the structure of the products prepared in the respective numbered Examples.
              TABLE 1                                                     
______________________________________                                    
MIC Values (γ/ml)                                                   
Fungi                                                                     
Compound Aspergillus Candida    Trichophyton                              
No.      fumigates   albicans M-9                                         
                                asteroides                                
______________________________________                                    
 1       3.1         6.2        <0.1                                      
 7       1.6         100.0      <0.1                                      
 8       1.6         25.0       50.0                                      
13       1.6         6.2        <0.1                                      
17       3.1         3.1        <0.1                                      
22       1.6         6.2        <0.1                                      
28       6.2         12.5       <0.1                                      
34       6.2         50.0       1.6                                       
39       0.4         6.2        <0.1                                      
40       12.5        25         1.6                                       
41       6.2         3.1        <0.1                                      
42       3.1         12.5       3.1                                       
43       1.6         12.5       3.1                                       
44       3.1         12.5       3.1                                       
45       6.2         25         3.1                                       
46       6.2         25         3.1                                       
47       6.2         12.5       1.6                                       
62       0.8         25.0       <0.1                                      
66       6.2         12.5       0.2                                       
67       6.2         6.2        0.2                                       
68       6.2         12.5       3.1                                       
69       12.5        25         1.6                                       
______________________________________
Compounds (I) and their acid addition salts exhibit excellent antifungal activities against various phytopathogenic fungi and soil borne pathogens and are useful as agricultural fungicides.
1. Control Test to Botrytis rot(gray mold) of Cucumber (1) Test Method
A seed of cucumber (cultivar:Matsukaze) was sown in a vinyl chloride-cup of 9 cm in diameter containing soil in a greenhouse and cultivated. At the primary leaf stage, 2.5 ml each of the solution containing a prescribed concentration of the test compound was applied over the above cucumber, which was kept at 25° to 26° C. in 80% humidity for 24 hours. A suspension of Botrytis cinerea spores was inoculated onto the leaves at five spots per leaf and the leaves were kept at 80° C. in 95% humidity for 72 hours.
(2) Results
The results are shown by percent disease control (%) calculated from the diseased degree according to the following formula. ##EQU1##
The compounds numbered in the following Table 2 each have the same structure as that of the compounds in the corresponding numbered Examples.
              TABLE 2                                                     
______________________________________                                    
Compd. Concentration            Percent Disease                           
No.    (ppm)       Diseased Degree                                        
                                Control (%)                               
______________________________________                                    
 1     500         0            100                                       
 3     "           "            "                                         
 6     "           "            "                                         
 7     "           40            60                                       
 8     "           0            100                                       
15     "           "            "                                         
17     "           "            "                                         
24     "           "            "                                         
27     "           "            "                                         
34     "           "            "                                         
61     "           "            "                                         
62     "           "            "                                         
un-    -           100           0                                        
treated                                                                   
______________________________________                                    
(Note)                                                                    
Diseased degrees were calculated according to                             
the subsequent formula:                                                   
Disease condition                                                         
                Marks   Numbers examined                                  
______________________________________                                    
Largely faded lesions                                                     
                20      a                                                 
formed at inoculated                                                      
parts                                                                     
Back of the inoculated                                                    
                10      b                                                 
leaf faded                                                                
Back of the inoculated                                                    
                5       c                                                 
leaf slightly faded                                                       
No disease      0       d                                                 
______________________________________                                    
 ##STR8##
A seed of cucumber (cultivar:Matsukaze) was sown on a vinyl chloride-cup of 9 cm in diameter in a greenhouse containing soil and cultivated. At the primary leaf stage, 2.5 ml each of the solution containing a prescribed concentration of the test compound was applied over the above cucumber, which was kept at 25° to 26° C. in 80% humidity for 24 hours. A suspension of Colletotrichum lagenarium spores was inoculated onto the above leaves at five spots per leaf and the leaves were kept at 25° C. in 95% humidity for 1 day and at 25° C. in 75 to 80% humidity for 6 days.
(2) Results
Percent disease control (%) was calculated as mentioned in the above test 1.
              TABLE 3                                                     
______________________________________                                    
Compd. Concentration            Percent Disease                           
No.    (ppm)       Diseased Degree                                        
                                Control (%)                               
______________________________________                                    
46     500         20           80                                        
58     "           0            100                                       
un-    -           100          0                                         
treated                                                                   
______________________________________
3. Control Test to Powdery Mildew of Cucumber (1) Test Method
A seed of cucumber (cultivar:Matsukaze) was sown in a vinyl chloride-cup of 9 cm in diameter containing soil in a greenhouse and cultivated. At the primary leaf stage, 5 ml each of a solution of the test compound in a prescribed concentration was applied over the above cucumber, which was kept at 25° to 26° C. for 1 day. Primary leaves of cucumber previously infected by pathogenic fungi of the powdery mildew (Shpaerotheca fuliginea) were taken and those having lesions covered with spores were cut out in 1 square centimeter pieces, which were stuck to the primary leaves in the cups for inoculation, four plots per leaf. The above treated leaves were kept at 25° to 26° C. for 10 days.
The spore formation on the inoculated plots was observed by a microscope.
Standard of the evaluation:
(+): Formation of many spores and hypae observed on the inoculated plots
(-): Neither infected spots nor spore formation observed on the inoculated plots
(2) Results 
______________________________________                                    
Compd. No. Concentration (ppm)                                            
                          Diseased Degree                                 
______________________________________                                    
 5         500            -                                               
21         "              -                                               
36         "              -                                               
78         "              -                                               
80         "              -                                               
untreated  -              +                                               
______________________________________
4. Control Test against rice plant blast (1) Test Method
Seedlings of rice plants (cultivar:Aichi-asahi) reared in a greenhouse for 10 days were transplanted in a vinyl chloride-cup of 9 cm in diameter. A solution of the test compound at a prescribed concentration was applied to the above rice plants 14 days after the transplanting. One day after the application, a spore suspension of pathogenic fungi of rice plant blast (Pyricularia oryzae) sprayed on the leaf blades of the seedlings, which were kept at 28° C. in 98% humidity for 24 hours and at 28° C. in 90% humidity for 7 days in a greenhouse. The number of infected spots on the inoculated leaves was observed.
(2) Results
The results are shown by percent disease control which was calculated according to the following formula: ##EQU2##
______________________________________                                    
Compd.  Concentration                                                     
                    Number of   Percent Disease                           
No.     (ppm)       Spots       Control (%)                               
______________________________________                                    
23      500         271         89.5                                      
28      "           45          98.3                                      
36      "           25          99.0                                      
78      "           99          96.2                                      
un-     -           2589        0                                         
treated                                                                   
______________________________________
V. How to Use
Compounds (I) or the salts thereof may be applied in a wide variety of oral or parenteral dosage forms solely or in admixture with additives such as diluents, carriers, dispersants and the like. The pharmaceutical compositions may be in the form of solutions, suspensions, powders, granules, tablets, injections, ointments, tinctures, and the like. The formulations may be dispensed in a conventional manner. For example, Compounds (I) may be administered at a dose of 100 to 2000 mg per day for enteral application.
Further, compounds (I) and the salts thereof exhibit an excellent control effect against the following phyto-pathogenic fungi and other soil borne pathogens.
Rice plant: blast, damping-off, leaf spot
Wheat and barley: stem rust, loose smut, powdery mildew
Pear: red spot, scab, Alternaria leaf spot
Grape: gray rust, ripe rot, downy mildew, leaf spot, white rot, gray mold, powdery mildew
Apple: Alternaria leaf spot, canker, black spot, red spot, blossom blight
Peach: brown rot
Cucumber: downy mildew, anthracnose, sclerotinia rot, gray mold, powdery mildew
Green pepper: powdery mildew
Tobacco: brown spot, powdery mildew
Compounds (I) or the salts thereof may be formed to wettable powders, granules, powders, emulsions, tablets, aerosols, fumigations, oils, and the like solely or into admixture with additives or carriers ordinarily employed in agricultural fungicides. Compounds (I) may be applied to plants at a dose of 0.5 to 100 g per are.
The following examples are provided to further illustrate this invention.
EXAMPLE 1 ##STR9## (step a)
To a solution of 60 g of imidazole in 300 ml of dry methylene chloride is added 26.2 g of thionyl chloride, and the mixture is stirred at room temperature for 10 minutes, mixed with 20 g of Compound (1), and stirred at room temperature for 1.5 hours. The reaction mixture is mixed with ice water and extracted with methylene chloride. The organic layer is washed with water, dried over Glauber's salt, and concentrated. The residue is dissolved in a mixture of 5% methanol and methylene chloride and chromatographed on a column of silica gel. The eluate is concentrated and the residue is washed with a mixture of ethyl acetate and isopropyl ether to give 25.8 g of Compound (2). mp. 150°-151° C.
IR: νmax Nujol 3300-2100, 2570, 1630 cm-1.
(step b)
To a solution of the sodium salt of Compound (2) prepared from 500 mg of Compound (2), 164 mg of 60% sodium hydride and 5 ml of dry dimethylformamide is added 828 mg of p-chlorobenzyl bromide, and the mixture is stirred at room temperature for 15 minutes. The reaction mixture is mixed with ice water and extracted with methylene chloride. The organic layer is washed with water, dried over Glauber's salt, and concentrated. The residue is chromatographed on a column of silica gel, which is eluted with a mixture of 2% methanol and methylene chloride. The eluate is collected and mixed with a mixture of hydrochloric acid and ethanol, and the mixture is concentrated. The residue is crystallized from a mixture of ethyl acetate and ether and recrystallized from a mixture of methanol and ethyl acetate to give 345 mg of Compound (3) hydrochloride.
mp. 180.5°˜181° C. (decomposition).
IR: νmax Nujol 2600 2300, 1649 cm-1.
EXAMPLE 2 ##STR10##
To a solution of N,N'-thionyldiimidazole prepared from 2.95 g of imidazole and 1.29 g of thionyl chloride in 15 ml of dry methylene chloride is added 2.0 g of Compound (4), and the mixture is extracted with methylene chloride. The organic layer is washed with water, dried over Glauber's salt, and concentrated. The residue is chromatographed on a column of silica gel, which is eluted with methylene chloride to recover 750 mg of unreacted Compound (4). The eluate from 1% methanol-methylene chloride to 2% methanol-methylene chloride is collected and concentrated, and the resulting residue is crystallized from ethanolic hydrochloric acid and recrystallized from methanol-ethyl acetate-ether to give 310 mg of Compound (5). mp. 153°-163° C.
EXAMPLE 3 ##STR11##
To a solution of 1 g of Compound (2) in 5 ml of dimethylformamide is added 322 mg of 60% suspension of sodium hydride in mineral oil with ice-cooling, and the mixture is stirred for 5 minutes, mixed with 1.14 g of methyliodide, and stirred at room temperature for 10 minutes. The reaction mixture is diluted with ice water and extracted with ether. The organic layer is washed with water, dried over Glauber's salt, and concentrated. The residue is chromatographed on a column of silica gel and eluted with 37% methanol-methylene chloride. The eluate is concentrated, and the residue is crystallized from hydrochloric acid-ethanol and recrystallized from methanol-acetic acid to give 520 mg of Compound (6).
mp. 190°-195° C.
Elemental Analysis (for C12 H12 ON2.HCl): Calcd(%): C, 60.89; H, 5.54; N, 11.84; Cl, 14.98; Found(%): C, 60.78; H, 5.52; N, 11.73; Cl, 15.02.
EXAMPLES 4 TO 91
The following compounds are prepared in the same manner as mentioned in the above Examples.
__________________________________________________________________________
 ##STR12##                                                                
Ex.                                                                       
No.                                                                       
   m X            Y    R.sup.1      R.sup.2  Saltup.3  mp (°C.) or 
                                                       IR                 
__________________________________________________________________________
4  0 --           2-O  CH.sub.2     CH.sub.3 --Im      164-165            
5  " "            "                                                       
                        ##STR13##   Ph  Im   "         155-156            
6  " "            "    C.sub.2 H.sub.5                                    
                                    CH.sub.2 HCl.1/2H.sub.2 O             
                                                       159-162            
7  " "            "    n-C.sub.3 H.sub.7                                  
                                    "        "         146-148            
8  " "            "    n-C.sub.4 H.sub.9                                  
                                    "        --        oily product       
                                                       v.sup.film 1638    
                                                       cm.sup.-1          
9  " "            "    (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    "        1/4CH.sub.3 OH               
                                                       oily product       
                                                       v.sup.film 1632    
                                                       cm.sup.-1          
10 " "            "    CH.sub.2 Ph  "        HCl       154-156            
11 " "            "                                                       
                        ##STR14##   "        --        85-86              
12 " "            "    "            "        HCl       180.5-181          
13 " "            "                                                       
                        ##STR15##   "        "         148.5-149          
14 " "            "                                                       
                        ##STR16##   "        "         161-163            
15 " "            "                                                       
                        ##STR17##   "        "         172-174            
16 " "            "                                                       
                        ##STR18##   "        --        94-94.5            
17 " "            "                                                       
                        ##STR19##   "        HCl       180-183            
18 " "            "                                                       
                        ##STR20##   "        "         138-147            
19 " "            "                                                       
                        ##STR21##   "        --        oily product       
                                                       v.sup.film 1639    
                                                       cm.sup.-1          
20 " "            "                                                       
                        ##STR22##   "        "         oily product       
                                                       v.sup.film 1630    
                                                       cm.sup.-1          
21 " "            "                                                       
                        ##STR23##   "        HCl       139-142            
22 " "            "                                                       
                        ##STR24##   "        "         165-172            
23 " "            "    (CH.sub.2).sub.2 Ph                                
                                    "        (COOH).sub.2                 
                                                       122.5-124.5        
24 " "            "    (CH.sub.2).sub.2N(C.sub. 2 H.sub.5).sub.2          
                                    "        2(COOH).sub.2                
                                                       80-81              
25 " "            "    (CH.sub.2).sub.2N(CH.sub.2 Ph).sub.2               
                                    "        --        oily product       
                                                       v.sup.film 1634    
                                                       cm.sup.-1          
26 " "            "                                                       
                        ##STR25##   "        2(COOH).sub.2                
                                                       153.5-155          
27 " "            "    (CH.sub.2).sub.2OPh                                
                                    "        HCl       158-160            
28 " "            "                                                       
                        ##STR26##   "        "         140-142            
29 " "            "    (CH.sub.2).sub.3Ph                                 
                                    "        --        oily product       
                                                       v.sup.film 1639    
                                                       cm.sup.-1          
30 " "            "    (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    "        2(COOH).sub.2                
                                                       125-127            
31 " "            "    (CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2           
                                    "        "         146.5-147.5        
32 " "            "                                                       
                        ##STR27##   "        --        oily product       
                                                       v.sup.film 1635    
                                                       cm.sup.-1          
33 " "            "                                                       
                        ##STR28##   "        HCl       138-140            
34 " "            "    CH.sub.3     CH CH.sub.3 *                         
                                             --        oily product       
                                                       v.sup.film 1660    
                                                       cm.sup.-1          
35 " "            "    CH.sub.2 Ph  CH CH.sub.3 ***                       
                                             "         oily product       
                                                       v.sup.film 1659    
                                                       cm.sup.-1          
36 " "            "                                                       
                        ##STR29##   CH CH.sub.3 *                         
                                             HCl       175-177            
37 " "            "    "            CH CH.sub.3 **                        
                                             "         185-187            
38 " "            "                                                       
                        ##STR30##   CH CH.sub.3 ***                       
                                             --        oily product       
                                                       v.sup.film 1658    
                                                       cm.sup.-1          
39 " "            "                                                       
                        ##STR31##   CH CH.sub.3 ***                       
                                             HCl       156-158            
40 " "            "    CH.sub.2 Ph  C(CH.sub.3).sub.2                     
                                             --        oily product       
                                                       v.sup.film 1665    
                                                       cm.sup.-1          
41 " "            "                                                       
                        ##STR32##   "        HCl       137-138            
42 " "            "                                                       
                        ##STR33##   "        --        62.5-64            
43 " "            "                                                       
                        ##STR34##   "        "         100-102            
44 " "            "                                                       
                        ##STR35##   "        "         100-101            
45 " "            "                                                       
                        ##STR36##   "        "         58-60              
46 " "            "    (CH.sub.2).sub.2OPh                                
                                    "        "         76-78              
47 " "            "                                                       
                        ##STR37##   "        "         oily product       
                                                       v.sup.film 1670    
                                                       cm.sup.-1          
48 1 4-Cl         "    CH.sub.3     CH.sub.2 HCl.1/2H.sub.2 O             
                                                       193-196            
49 " "            "                                                       
                        ##STR38##   "        --        132-133            
50 " "            "    (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    "        2(COOH).sub.2                
                                                       142-143.5          
51 " 5-Cl         "                                                       
                        ##STR39##   H  Ph    --        115-116            
52 " "            "    CH.sub.2 Ph  Ph  Im   --        166.5-167          
53 " "            "                                                       
                        ##STR40##   Ph  Im   --        187-188            
54 " "            "                                                       
                        ##STR41##   Ph  Im   --        189-191            
55 " "            "                                                       
                        ##STR42##   Ph  Im   --        165-167            
56 " "            "                                                       
                        ##STR43##   Ph  Im   --        172-173.5          
57 " "            "    CH.sub.2 Ph  CH.sub.2 HCl.1/10H.sub.2 O            
                                                       174-175            
58 " "            "                                                       
                        ##STR44##   "        "         188-190            
59 " "            "                                                       
                        ##STR45##   "        HCl.H.sub.2 O                
                                                       172-174            
60 " "            "                                                       
                        ##STR46##   "        HCl       165-172            
61 " "            "    CH.sub.3     "        "         239                
62 " "            "    n-C.sub.3 H.sub.7                                  
                                    "        "         178-181            
63 " "            "    CH.sub.2 Ph  CH CH.sub.3 ***                       
                                             "         132-134            
64 " "            "                                                       
                        ##STR47##   "        "         211-212            
65 " "            "                                                       
                        ##STR48##   "        "         170-174            
66 " "            "    CH.sub.2 Ph  C(CH.sub.3).sub.2                     
                                             "         192-193.5          
67 " "            "                                                       
                        ##STR49##   "        "         201-203            
68 " "            "                                                       
                        ##STR50##   "        "         193-194            
69 " "            "                                                       
                        ##STR51##   "        --        106-108            
70 " "            "                                                       
                        ##STR52##   "        1/3H.sub.2 O                 
                                                       oily product       
                                                       v.sup.film 1668    
                                                       cm.sup.-1          
71 " "            "    CH.sub.3     CH Ph    --        118-118.5          
72 " "            "    CH.sub.2 Ph  CH C.sub.2 H.sub.5 ***                
                                             --        158.5-159.5        
73 " "            "                                                       
                        ##STR53##   CH C.sub.2 H.sub.5 ***                
                                             HCl       220-222            
74 " "            "                                                       
                        ##STR54##   CH C.sub.2 H.sub.5 ***                
                                             HCl       166-167            
75 " "            "    (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    CH.sub.2 2(COOH).sub.2                
                                                       105.5-107          
76 "                                                                      
      ##STR55##   "                                                       
                        ##STR56##   "        HCl       193-195            
77 2 3,5-Cl       "    CH.sub.2 Ph  "        "         170-172            
78 " "            "                                                       
                        ##STR57##   "        "         155-165            
79 " "            "                                                       
                        ##STR58##   "        "         170-171            
80 " "            "                                                       
                        ##STR59##   "        "         150-153.5          
81 " "            "                                                       
                        ##STR60##   "        2(COOH).sub.2.1/3H.sub.2     
                                                       153-154            
82 " "            "    (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    "        2(COOH).sub.2                
                                                       119-120            
83 0 --           3-O                                                     
                        ##STR61##   "        1/2H.sub.2 O                 
                                                       oily product       
                                                       v.sup.film : 1638  
                                                       cm.sup.-1          
84 " "            2-NH "            CH.sub.3 --Im      143.5-144          
85 " "            "    "            CH.sub.2 "         147-148            
86 " "                                                                    
                   ##STR62##                                              
                       "            "        "         101-101.5          
87 1 5-Cl         2-O  (CH.sub.2).sub.3N(CH.sub.3).sub.2                  
                                    C(CH.sub.3).sub.2                     
                                             2(COOH).sub.2.CH.sub.3       
                                                       101-104            
88                                                                        
    ##STR63##     "                                                       
                        ##STR64##   H  H     HCl       166-167            
89                                                                        
    ##STR65##     "    "            H  H     --        154-156            
90                                                                        
    ##STR66##     "    "            H  H     "         142-143            
91                                                                        
    ##STR67##     "    "            CH.sub.2 --        120-121            
__________________________________________________________________________
 (Note)                                                                   
 The meanings of abbreviations are as follows:                            
 Ph = phenyl Im = imidazolyl iPr = isopropyl Tr = trifluoroacetyl         
 *means that methyl (ethyl, phenyl) group takes cisform to imidazolyl     
 group.                                                                   
 **means that methyl (ethyl, phenyl) group takes transform to imidazolyl  
 group.                                                                   
 ***means the mixture of cis and transform.
REFERENCE EXAMPLE 1 ##STR68##
Compound (2) (500 mg) is hydrogenated in 14% hydrochloric acid-methanol (5 ml) in the presence of platinum oxide in a hydrogen stream. After the absorption of 1 mole of hydrogen, the reaction is stopped. The reaction is filtered and the filtrate is concentrated. The residue is mixed with aqueous sodium hydrogencarbonate solution and extracted with methylene chloride. The organic layer is washed with water, dried over Glauber's salt and concentrated. The residue is crystallized from ethyl acetate-isopropyl ether to give Compound (7) (456 mg).
mp. 170.5°˜172° C.
REFERENCE EXAMPLE 2 ##STR69##
To a solution of N,N'-thionyldiimidazole prepared from imidazole (4.12 g), thionyl chloride (1.8 g), and dry methylene chloride (20 ml) is added Compound (1) (2 g), and the mixture is allowed to stand at room temperature overnight. The reaction mixture is mixed with ice-water and extracted with methylene chloride. The organic layer is washed with water, dried, and concentrated. The residue is washed with ethyl acetate-ether to give Compound (9) (2.72 g).
mp. 183°˜193° C.
Hydrochloride of Compound (9) (2HCl.H2 O).
mp. 124°˜127° C.
The preparations for fungicides are as follows:
Preparation 1
A mixture of Compound (3) hydrochloride prepared in Example 1 (5 weight parts), clay (85 weight parts), and talc (10 weight parts) is pulverized and formulated into a dust.
Preparation 2
A mixture of a compound prepared in Example 8 (50 weight parts), diatomaceous earth (45 weight parts), and calcium alkylbenzenesulfonate (2.5 weight parts) is pulverized, admixed, and formulated into a wettable powder.
Preparation 3
A mixture of the compound prepared in Example 27 (30 weight parts), xylene (60 weight parts), and polyoxyethylene alkyl aryl ether (10 weight parts) is admixed and formulated into an emulsion.
Preparation 4
A mixture of the compound prepared in Example 3 (5 weight parts), clay (85 weight parts), and talc (10 weight parts) is pulverized and formulated into a dust.
Preparation 5
A mixture of the compound prepared in Example 48 (50 weight parts), diatomaceous earth (45 weight parts), and calcium alkylbenzenesulfonate (2.5 weight parts) is pulverized, admixed, and formulated into a wettable powder.
Preparation 6
A mixture of the compound prepared in Example 7 (30 weight parts), xylene (60 weight parts), and polyoxyethylene alkyl aryl ether (10 weight parts) is admixed and formulated into an emulsion.
Preparation 7
The compound prepared in Example 62 (10 weight parts) is dissolved in water (90 weight parts) to give a solution.
The preparations for antimycotics are as follows:
Preparation 8 
______________________________________                                    
Cream:                                                                    
      The compound prepared in Example 13                                 
                                10     g                                  
      Bees wax                  100    g                                  
      Cetyl alcohol             50     g                                  
      2-Octyldodecanol          50     g                                  
      Propylene glycol          300    g                                  
      Mixture (1:1 w/w) of sorbitan mono-                                 
                                50     g                                  
      stearate and polyoxyethylene sorbitan                               
      monostearate                                                        
      Mixture (1.9:0.2 w/w) of butyl paraben                              
                                2      g                                  
      and methyl paraben                                                  
      Mixture (0.06:1.25:9 w/w/w) of phosphoric                           
                                10     g                                  
      acid, sodium hydroxide and monosodium                               
      phosphate dihydrate                                                 
      Distilled water           428    g                                  
                                1000   g                                  
______________________________________
Preparation 9 
______________________________________                                    
Gel:   Nitrate of the compound prepared in                                
                              10     g                                    
       Example 13                                                         
       Carbopol 940 (carboxyvinyl polymer)                                
                              15     g                                    
       Ethanol                100    g                                    
       Propylene glycol       650    g                                    
       Triisopropanolamine    10     g                                    
       Distilled water        215    g                                    
                              1000   g                                    
______________________________________

Claims (9)

What we claim is:
1. A compound of the formula: ##STR70## wherein X is halogen;
m is an integer of 0 to 3;
n is an integer of 0 to 4;
Q is phenyl optionally substituted by 1 to 3 members selected from the group consisting of halogen, C1 -C5 alkyl and C1 -C5 alkoxy; and ##STR71## is 1-(1-imidazolyl)-1-phenylmethylene, or a pharmaceutically acceptable acid addition salt thereof.
2. The compound 1-[2-(4-chlorobenzyloxy)phenyl]-1,1-bis(1-imidazolyl)-1-phenylmethane.
3. The compound 1-(2-benzyloxy-5-chlorophenyl)-1,1-bis(1-imidazolyl)-1-phenylmethane.
4. The compound 1-[5-chloro-2-(4-chlorobenzyloxy)phenyl]-1,1-bis(1-imidazolyl)-1-phenylmethane.
5. The compound 1-[5-chloro-2-(4-methylbenzyloxy)phenyl]-1,1-bis(1-imidazolyl)-1-phenylmethane.
6. The compound 1-[5-chloro-2-(2,4-dichlorobenzyloxy)phenyl]-1,1-bis(1-imidazolyl)-1-phenylmethane.
7. The compound 1-[5-chloro-2-(3,4-dichlorobenzyloxy)phenyl]-1,1-bis(1-imidazolyl)-1-phenylmethane.
8. A fungicidal composition for agricultural application containing an effective fungicidal amount of the compound of claim 1 together with one or more inert carriers and/or adjuvants.
9. A method for controlling phytopathogenic fungi and other soil-borne pathogens which comprises applying the fungicidal composition of claim 8 to agricultural plants and/or fields.
US06/341,634 1979-06-07 1982-01-22 Bis-imidazolyl-bis-phenylmethane derivatives and their use as fungicides Expired - Lifetime US4463011A (en)

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JP54071953A JPS6011904B2 (en) 1979-06-07 1979-06-07 1-benzylimidazole derivative
JP54-71953 1979-06-07
JP54-115465 1979-09-07
JP11546579A JPS5639073A (en) 1979-09-07 1979-09-07 1- alpha-styryl imidazole

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880804A (en) * 1988-01-07 1989-11-14 E. I. Du Pont De Nemours And Company Angiotensin II receptor blocking benzimidazoles
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US5135943A (en) * 1984-02-02 1992-08-04 Ferrer Internacional S.A. 1H-imidazole derivative compounds and pharmaceutical compositions containing the same
US5155118A (en) * 1986-07-11 1992-10-13 E. I. Du Pont De Nemours And Company Method and composition for preventing NSAID-induced renal failure
US5138069A (en) * 1986-07-11 1992-08-11 E. I. Du Pont De Nemours And Company Angiotensin II receptor blocking imidazoles
US5153197A (en) * 1986-07-11 1992-10-06 E. I. Du Pont De Nemours And Company Treatment of hypertension with angiotensin II blocking imidazoles
US5128355A (en) * 1986-07-11 1992-07-07 E. I. Du Pont De Nemours And Company Treatment of congestive heart failure with angiotensin 11 receptor blocking imidazoles
US4943585A (en) * 1987-05-02 1990-07-24 Basf Aktiengesellschaft N-substituted azoles and insecticide, arachnicide, and nematocide compositions thereof
US4880804A (en) * 1988-01-07 1989-11-14 E. I. Du Pont De Nemours And Company Angiotensin II receptor blocking benzimidazoles
US5210079A (en) * 1988-01-07 1993-05-11 E. I. Du Pont De Nemours And Company Treatment of chronic renal failure with imidazole angiotensin-II receptor antagonists
US5354867A (en) * 1988-12-06 1994-10-11 E. I. Du Pont De Nemours And Company Angiotensin II receptor blocking imidazoles
US5254546A (en) * 1989-06-30 1993-10-19 E. I. Du Pont De Nemours And Company Fused aryl substituted imidazole angiotensin II receptor inhibitors
US5466704A (en) * 1991-02-26 1995-11-14 E. R. Squibb & Sons, Inc. N-substituted imidazole and benzimidazole derivatives useful as angiotenson II antagonists
US5965743A (en) * 1994-04-27 1999-10-12 Nippon Soda Co., Ltd. N-substituted imidazol derivative
US20060211845A1 (en) * 2003-04-16 2006-09-21 Huntsman Advanced Materials Americas Inc. 1-Imidazolymethyl -substituted -2-naphtols and their use as accelerators for low - temperature curing
US7468441B2 (en) * 2003-04-16 2008-12-23 Hunstman Advanced Materials Americas Inc. 1-imidazolymethyl-substituted-2-naphtols and their use as accelerators for low-temperature curing
KR101158270B1 (en) * 2003-04-16 2012-06-20 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 1-imidazolylmethyl-substituted-2-naphtols and their use as accelerators for low-temperature curing

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GB2118549B (en) 1984-04-11
DK157860B (en) 1990-02-26
IT8067889A0 (en) 1980-06-06
DE3021467C2 (en) 1989-11-02
IE801159L (en) 1980-12-07
GB2054560A (en) 1981-02-18
GB2054560B (en) 1983-09-01
DK239980A (en) 1980-12-08
NL184003B (en) 1988-10-17
NL184003C (en) 1989-03-16
SE8004194L (en) 1980-12-08
NL8003310A (en) 1980-12-09
FR2458545A1 (en) 1981-01-02
AR230184A1 (en) 1984-03-01
FR2458545B1 (en) 1986-04-18
US4483866A (en) 1984-11-20
DE3021467A1 (en) 1980-12-18
SE453991B (en) 1988-03-21
US4328348A (en) 1982-05-04
AR226847A1 (en) 1982-08-31
IT1129813B (en) 1986-06-11
IL60252A0 (en) 1980-09-16
IL60252A (en) 1987-02-27
CA1141388A (en) 1983-02-15
CH646693A5 (en) 1984-12-14
HU188607B (en) 1986-04-28
MX5880E (en) 1984-08-16
IE49604B1 (en) 1985-10-30
DK157860C (en) 1990-07-30

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